Bis(2-fluoro-2 2-dinitroethyl amides

ABSTRACT

AMIDES OF 2-FLUORO-2,2-DINITROETHYLAMINE FORMED BY REACTING 2-FLUORO-2,2-DINITROETHYLAMINE WITH A MONO- OR BIFUNCTIONAL ACID HALIDE IN THE PRESENCE OF PYRIDINE.

United States Patent 3,644,519 BIS(2-FLUOR0-2,2-DINITROETHYL AMIDESHorst G. Adolph, Beltsville, and Mortimer J. Kamlet,

Silver Spring, Md., assignors to the United States of America asrepresented by the Secretary of the Navy No Drawing. Filed Jan. 2, 1969,Ser. No. 790,509 Int. Cl. C07c 103/30 US. Cl. 260-561 K 2 ClaimsABSTRACT OF THE DISCLOSURE Amides of 2-fluoro-2,2-dinitroethylamineformed by reacting 2-fiuoro-2,2-dinitroethylamine with a monoorbifunctional acid halide in the presence of pyridine.

BACKGROUND OF THE INVENTION SUMMARY OF THE INVENTION Accordingly, anobject of this invention is to provide novel fluorodinitro compounds.

Another object of the invention is to provide highly thermally stableexplosives.

Briefly, in accordance with this invention, these and other objects areattained by reacting 2-fluoro-2,2-dinitroethylamine with an acid halidein the presence of pyridine.

DESCRIPTION 0F THE PREFERRED EMBODIMENTS The preparation of thecompounds which are within the scope of the invention involves the useof 2-fluoro-2,2- dinitroethylamine as a starting material. This compoundcan be made by various methods as disclosed in copending application,Ser. No. 790,510, filed Ian. 2, 1969. The amine is then reacted with anyacid chloride, either monoor bifunctional, under basic conditions toobtain the resulting amide. The following examples are included forpurposes of illustration and are not intended to limit the scope of theinvention.

EXAMPLE I Phosgene gas is bubbled for a period of 2 hours into arefluxing solution of 5.1 g. of 2-fiuoro-2,2-dinitroethylamine and 3.0g. of pyridine in 50 ml. of methylene chloride. After the reaction iscompleted, petroleum ether is added and the product is filtered 10K andwashed thoroughly with water to give 5.1 g. (92% yield) of bis(2-fiuoro-2,2-dinitroethyl) urea. The melting point of the product afterrecrystallization from an ethyl acetate-toluene mixture is 185-'6 C.

3,644,519 Patented Feb. 22, 1972 ice Analysis for C H F N O .Calculated:N, 25.31%; F, 11.42%; MW, 332. Found: N, 25.3%; F, 11.6%; MW (MEK)325.

EXAMPLE II 2.85 g. of oxalyl chloride in 10 ml. of methylene chloride isadded to a solution of 6.9 g. 2-fiuoro-2,2-dinitroethylamine and 3.55 g.of pyridine in 60 ml. of methylene chloride. This mixture is thenstirred for 3 hours at room temperature, refluxed for 1 hour and pouredinto dilute sulfuric acid. The methylene chloride is evaporated and thecrude product filtered off. The product obtained was 7.4 g. (91%) bis(2fiuoro 2,2 dinitroethyl) oxamide which melted after recrystallizationfrom chloroformacetone at 224-5 C.

Analysis for C H F N O Calculated (percent) N, 23.34; F, 10.55. Found(percent): N, 22.6; F, 10. 6.

EXAMPLE III The same procedure is followed as in Example II except thatmalonyl chloride in dry methylene chloride is used in place of oxalylchloride and the residue is washed with water. The productbis(2-fluoro-2,2-dinitroethyl) malonamide is obtained in over yield.

Many of the resulting amides not only exhibit excel lent thermalstability at temperatures up to and above 200 C. but they have highdensities which indicate that the compounds would be of use where highdetonation pressures are desired. For example, the oxamide in Example IIcan withstand heating to C. for at least 168 hours, to C. for at least72 hours and to 200 C. for several hours without visible signs ofdecomposition, an appreciable weight loss or a depression in meltingpoint. The crystal density of the compounds prepared in Examples I andII are 1.86 and 1.90 respectively.

Various acid halides can be used in the practice of this invention. Forexample, acid bromides may be used in place of the acid chlorides of theexamples. Also other dibasic acid halides are alternatives and theyinclude such compounds as succinyl and glutaryl halides.

Obviously, numerous other modifications and variations of the presentinvention are possible in light of the above teachings. It is thereforeto be understood that within the scope of the appended claims theinvention may be practiced otherwise than as specifically describedherein.

What is claimed as new and desired to be secured by Letters Patent ofthe United States is:

l. The compound, bis(2-fluoro-2,2-dinitroethyl)oxalnide.

2. The compound, bis(2-fluoro-2,2-dinitroethyl) malonamide.

References Cited UNITED STATES PATENTS 3,000,945 9/ 1961 Frankel 260-561ELBERT L. ROBERTS, Primary Examiner E. 6. LOVE, Assistant Examiner US.Cl. X.R. 260-553 R

